Efficient Telomerization of Butadiene with Starch in Water: The Role of the Surfactant

The synthesis of hydrophobic starch was performed via palladium-catalyzed telomerization of butadiene with native starch. This reaction is efficiently performed in water in the presence of neutral or cationic surfactant with high HLB. After optimization of the reaction conditions, TOF up to 446 was achieved.     

Incorporating a Polyethyleneglycol Linker to Enhance the Hydrophilicity of Mitochondria-Targeted Triphenylphosphonium Constructs

The targeting of bioactive molecules and probes to mitochondria can be achieved by coupling to the lipophilic triphenyl phosphonium (TPP) cation, which accumulates several hundred-fold within mitochondria in response to the mitochondrial membrane potential (Δψ_m). Typically, a simple alkane links the TPP to its “cargo”, increasing overall hydrophobicity. As it would be beneficial to enhance the water solubility of mitochondria-targeted compounds we explored the effects of replacing the alkyl linker with a polyethylene glycol (PEG). We found that the use of PEG led to compounds that were readily taken up by isolated mitochondria and by mitochondria inside cells. Within mitochondria the PEG linker greatly decreased adsorption of the TPP constructs to the matrix-facing face of the mitochondrial inner membrane. These findings will allow the distribution of mitochondria-targeted TPP compounds within mitochondria to be fine-tuned.     

Adaptation of machining toolpath to distorted geometries: application to remove a constant thickness on rough casting prosthesis

This study proposes a method to adapt the geometry of the toolpath to a specified target. In the case study presented, the geometrical target is to remove a constant thickness on the rough workpiece. This case is normally present in the polishing of the femoral component of knee prostheses. In fact, an operator carries out these operations manually. The aim of this study is to contribute to the automation of prosthesis production, notably, in the preparation of surface polishing. The proposed method can deform and adapt a toolpath to ensure the required geometry of the machined surface. The proposed toolpath deformation method is composed of three steps: alignment, toolpath deformation, and toolpath smoothing. Alignment between the measured surface of the roughcast prostheses and the nominal toolpath is carried out by an Iterative Closest Point (ICP) algorithm. The principle of this algorithm is to find the optimal rigid transformation to readjust the toolpath on the measured surface. Subsequently, the toolpath is deformed to remove the constant thickness of the roughcast prostheses. Next, to increase the machined quality, a smoothing stage is carried out on the obtained toolpath. Experimental tests on industrial prostheses geometry are conducted to validate the effectiveness of this method.     

Identification of asymmetric constitutive laws at high temperature based on Digital Image Correlation

The mechanical characterization of ceramics can be very challenging. Depending on their composition and fabrication process, ceramic materials may exhibit at room temperature different types of mechanical behaviours, ranging from linear elastic to quasi-brittle, like rocks, concrete or plasters. At elevated temperature, they may present a non-linear behaviour, due for instance to the presence of a vitreous phase. However, estimating the evolution of their behaviour from room temperature to elevated temperature is a challenging topic, especially when there is an asymmetry between tension and compression. A methodology based on Digital Image Correlation is presented in this paper where four point bending tests are analysed for temperatures ranging from 25 °C to 900 °C. For a ceramic mainly made of aluminium titanate, the evolution of an asymmetric constitutive law is identified with a strong link with microstructural observations using SEM images.     

Robust scene recognition using a GA and real-world raw-image

This paper presents a new concept of scene recognition by a genetic algorithm (GA), using the 2-D gray-scale image of a working space, termed here as raw-image, and a model shaping the 2-D top-surface of a target object. In fact here, the problem of object recognition in the raw-image is changed into an optimization problem of a model-based evaluation function. We make use in this research of a GA, as a search and optimization method. This GA employs a model-based fitness function as its objective function to perform the search of a target in the raw-image. In this research, three object models, namely a frame model, a surface model, and a surface-strips model are investigated in order to determine which one is the best for scene recognition in a noisy environment. Also, in order to appraise the recognition performance of each model, a comparative study is performed by analyzing the answers to the following criteria questions: sensitivity, reliability, and speed. The effectiveness of the method has been verified through experiments using real-world raw-images, and the method has shown its robustness of object recognition with the surface-strips model, in spite of the noises in the scene.     

Multichannel AR parameter estimation from noisy observations as an errors-in-variables issue

In various applications from radar processing to mobile communication systems based on CDMA or OFDM, M-AR multichannel processes are often considered and may be combined with Kalman filtering. However, the estimations of the M-AR parameter matrices and the autocorrelation matrices of the additive noise and the driving process from noisy observations are key problems to be addressed. In this paper, we suggest solving them as an errors-in-variables issue. In that case, the noisy-observation autocorrelation matrix compensated by a specific diagonal block matrix and whose kernel is defined by the M-AR parameter matrices must be positive semi-definite. Hence, the parameter estimation consists in searching every diagonal block matrix that satisfies this property, in reiterating this search for a higher model order and then in extracting the solution that belongs to both sets. A comparative study is then carried out with existing methods including those based on the Extended Kalman Filter (EKF) and the Sigma-Point Kalman Filters (SPKF). It illustrates the relevance and advantages of the proposed approaches.     

Structural and magnetic properties of Lix(MnyFe1−y)PO4 electrode materials for Li-ion batteries

A series of LiMn_yFe_1−yPO₄ samples have been prepared in the whole range 0 ≤ y ≤ 1. Chemical delithiation could be achieved to obtain Mn_yFe_1−yPO₄ in the range 0 ≤ y ≤ 0.8, keeping the same crystal phase (olivine structure, space group Pnma). The composition y = 0.8 is the limit where the delithiated phase is still crystallized, but abruptly suffers strains at the molecular scale evidenced by both optical spectroscopy and X-ray diffraction. The analysis of the magnetic properties shows that in all the samples the concentration of impurities is negligible. The concentration of polarons, either holes associated to Li vacancies in LiMn_yFe_1−yPO₄ or electrons associated to the existence of Li left in the matrix of Mn_yFe_1−yPO₄, is found to be small (≤1%) in all the samples. For y ≤ 0.6, all the Mn³⁺ ions Mn_yFe_1−yPO₄ are in the high-spin state (S = 2). At larger manganese concentration, however, the Mn³⁺ ions in excess of the critical concentration y_c = 0.6 undergo a transition to the low-spin state (S = 1). As a consequence, and in contrast with prior works, we find that Mn_0.8Fe_0.2PO₄ has magnetic interactions that are much smaller, and no antiferromagnetic ordering in this compound is detected, at least above 20 K. Antiferromagnetic ordering that had been reported so far for Mn_yFe_1−yPO₄ at large y-composition might come from incomplete delithiation. The spin-transition of Mn³⁺ in concentration (y–y_c) to the low-spin state is at the origin of the strain fields at the molecular scale that increase with y for y > 0.6, and ultimately prevents the full delithiation for y > 0.8. This result sheds light on the reason for the degradation of cathode properties in Mn-rich compounds of the heterosite–purpurite series, while the electrochemical properties are good in the range y ≤ 0.6 but only at slow rates, due to the very small hopping mobility of the small polaron.     

An efficient reduced simulation of residual stresses in composite forming processes

An efficient simulation of thermal and mechanical models involved in thermosetting composites forming needs to overcome some numerical difficulties related to: (i) the multi-scale behaviour; (ii) the complex geometries involved needing too many degrees of freedom; (iii) the large time intervals where the solution has to be computed; (iv) the non-linearity of the involved evolution equations; (v) the numerous couplings… In this work, an efficient strategy based on a separated representation is proposed. This method enables to avoid the use of an incremental strategy and can lead to impressive computing time savings especially when the model involves fine meshes and very small time steps. The local non-linear chemical kinetics and its coupling with the global heat balance equation are naturally introduced in the separated representation algorithm. Moreover, the dependence of the thermal conductivity and the specific heat on the temperature and on the reaction advancement degree are also taken into account. Knowing the history of the temperature field, the separated representation is again used to solve the thermo-mechanical problem in order to determine the residual stresses.     

Determination of surface-induced platelet activation by applying time-dependency dissipation factor versus frequency using quartz crystal microbalance with dissipation

Platelet adhesion and activation rates are frequently used to assess the thrombogenicity of biomaterials, which is a crucial step for the development of blood-contacting devices. Until now, electron and confocal microscopes have been used to investigate platelet activation but they failed to characterize this activation quantitatively and in real time. In order to overcome these limitations, quartz crystal microbalance with dissipation (QCM-D) was employed and an explicit time scale introduced in the dissipation versus frequency plots (Df–t) provided us with quantitative data at different stages of platelet activation. The QCM-D chips were coated with thrombogenic and non-thrombogenic model proteins to develop the methodology, further extended to investigate polymer thrombogenicity. Electron microscopy and immunofluorescence labelling were used to validate the QCM-D data and confirmed the relevance of Df–t plots to discriminate the activation rate among protein-modified surfaces. The responses showed the predominant role of surface hydrophobicity and roughness towards platelet activation and thereby towards polymer thrombogenicity. Modelling experimental data obtained with QCM-D with a Matlab code allowed us to define the rate at which mass change occurs (A/B), to obtain an A/B value for each polymer and correlate this value with polymer thrombogenicity.